Design and Synthesis of Benzosultine-sulfone as a o-Xylylene

May 24, 2010 - It is worth mentioning that here the temperature of the reaction is used as regiocontrol element. ... Generally, thermal activation of ...
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Design and Synthesis of Benzosultine-sulfone as a o-Xylylene Precursor via Cross-enyne Metathesis and Rongalite: Further Expansion to Polycyclics via Regioselective Diels-Alder Reaction

DA strategy, we had reported a novel synthetic approach to various new o-xylylene (o-quinodimethane) intermediates such as 73 and 8.4

Sambasivarao Kotha* and Arjun S. Chavan Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India [email protected] Received April 6, 2010 FIGURE 1. Approaches toward the generation of o-quinodimethane 1.

Transient intermediates related to o-quinodimethane (o-QDM) or o-xylylene1 1 have expanded the Diels-Alder (DA) strategy.2 Diverse approaches toward the generation of 1 either by thermal (Figure 1) or photochemical means are available. To expand the

Although the thermal ring opening of benzosulfone5 2, benzosultine6 3, and benzocyclobutene7 4 generates the o-xylylene 1, benzosultine 3 opens up at relatively low temperature as compared with the other o-xylylene precursors such as 2 and 4. Dittmer and co-workers had reported the synthesis of the sultine derivative (1,4-dihydro-2,3-benzoxathiin-3-oxide) 3 from o-xylylene dibromide in high yield under phase-transfer catalyst (PTC) conditions using rongalite. They had also demonstrated the generation of o-xylylene intermediate 1 at relatively low temperature.8 Generally, sultine derivatives are prepared from the corresponding R,R0 -dibromoxylenes via rongalite at low temperature, and the corresponding sulfones are prepared by heating the sultines in the absence of trapping agents in a sealed tube9 or oxidation of corresponding sulfides.10 On some occasions it was reported that the pyrolysis of benzosulfone derivatives gave benzocylcobutenes by extrusion of sulfur dioxide.11 Rongalite (sodium hydroxymethanesulfinate or sodium formaldehyde sulfoxylate) is commercially available material used in the textile industry as a decolorizing agent, and it has also been used in organic synthesis.12 In view of our interest in designing polycyclics and unusual R-amino acid (AAA) derivatives via rongalite,13 we

(1) (a) Segura, J. L.; Martin, N. Chem. Rev. 1999, 99, 3199. (b) Martin, N.; Seoane, C.; Hanack, M. Org. Prep. Proc. Int. 1991, 23, 237. (c) Charlton, J. L.; Alauddin, M. M. Tetrahedron 1987, 43, 2873. (d) Funk, R. L.; Vollhardt, K. P. C. Chem. Soc. Rev. 1980, 9, 41. (e) McCullough, J. J. Acc. Chem. Res. 1980, 13, 270. (f) Quinkert, G.; Stark, H. Angew. Chem., Int. Ed. 1983, 22, 637. (g) Oppolzer, W. Synthesis 1978, 793. (h) Bieber, L. W; da Silva, M. F. Molecules 2001, 6, 472. (2) (a) Fringuelli, F.; Taticchi, A. In Dienes in the Diels-Alder Reaction; Wiley: New York, 1990. (b) Paquette, L. A. In Comprehensive Organic Synthesis; Pergmon: Oxford, U.K., 1991; Vol. 5. (c) Carruthers, W. In Tetrahedron Organic Chemistry Series, Cycloaddition Reactions in Organic Synthesis; Baldwin, J. E., Magnus, P. D., Eds.; Pergamon: Oxford, U.K., 1990; Vol. 8. (3) Kotha, S.; Ghosh, A. K. Tetrahedron 2004, 60, 10833. (4) Kotha, S.; Khedkar, P. J. Org. Chem. 2009, 74, 5667. (5) (a) Tanaka, K.; Kaji, A. In The Chemistry of Sulphones and Sulphoxides; Patai, S., Rappoport, Z., Stirling, C., Eds.; John Wiley: New York, 1988; pp 729-821. (b) Simpkins, N. S. In Tetrahedron Organic Chemistry Series; Baldwin, J. E., Magnus, P. D., Eds.; Pergamon: Oxford, U.K.; Vol. 10, Sulphones in Organic Synthesis, 1993. (6) Dittmer, D. C.; Hoey, M. D. In The Chemistry of Sulphinic Acids, Esters, and Their Derivatives; Patai, S., Ed.; Wiley: Chichester, U.K., 1990; pp 239-273. (7) (a) Klundt, I. L. Chem. Rev. 1970, 70, 471. (b) Kametani, T.; Fukumoto, K. Acc. Chem. Res. 1976, 9, 319. (c) Thummel, R. P. Acc. Chem. Res. 1980, 13, 70. (d) Gandhi, P. J. Sci. Ind. Res. 1982, 495. (e) Michellys, P.-Y.; Pellissier, H.; Santelli, M. Org. Prep. Proced. Int. 1996, 28, 545. (f) Mehta, G.; Kotha, S. Tetrahedron 2001, 57, 625. (g) Kametani, T.; Nemoto, H. Tetrahedron 1981, 37, 3. (h) Matsuya, Y.; Qin, H.; Nagaoka, M.; Nemoto, H. Heterocycles 2004, 62, 207.

(8) Hoey, M. D.; Dittmer, D. C. J. Org. Chem. 1991, 56, 1947. (9) (a) Jung, F.; Molin, M.; Van Den Elzen, R.; Durst, T. J. Am. Chem. Soc. 1974, 96, 935. (b) Kotha, S.; Ghosh, A. K. Ind. J. Chem. Sec. B 2006, 45B, 227. (c) Kotha, S.; Ghosh, A. K. Synthesis 2004, 558. (10) (a) Cava, M. P.; Shirley, R. L. J. Am. Chem. Soc. 1960, 82, 654. (b) Mann, J.; Piper, S. E. J. Chem. Soc., Chem. Commun. 1982, 430. (c) Cava, M. P.; Mitchell, M. J.; Deana, A. A. J. Org. Chem. 1960, 25, 1481. (11) (a) Cava, M. P.; Shirley, R. L.; Erickson, B. W. J. Org. Chem. 1962, 27, 755. (b) Cava, M; Deana, A. A.; Muth, K. J. Org. Chem. 1960, 82, 2524. (12) (a) Messinger, P.; Greve, H. Synthesis 1977, 259. (b) Huang, B.-N.; Haas, A.; Lieb, M. J. Fluorine Chem. 1987, 36, 49. (c) Jarvis, W. F.; Hoey, M. D.; Finocchio, A. L.; Dittmer, D. C. J. Org. Chem. 1988, 53, 5750. (d) Huang, B.; Liu, J.; Huang, W. J. Chem. Soc., Chem. Commun. 1990, 1781. (e) Huang, B.; Liu, J. Tetrahedron Lett. 1990, 31, 2711. (f) Huang, B.-N.; Liu, J.-T. J. Fluorine Chem. 1993, 64, 37. (g) Dolbier, W. R., Jr.; Medebielle, M.; Ait-Mohand, S. Tetrahedron Lett. 2001, 42, 4811. (h) Saikia, A. K.; Tsuboi, S. J. Org. Chem. 2001, 66, 643. (i) Tang, R.-Y.; Zhong, P.; Lin, Q.-L. Synthesis 2007, 85. (j) Harris, A. Synth. Commun. 1987, 17, 1587. (k) Harris, A. Synth. Commun. 1988, 18, 659. (l) Harris, A. R.; Mason, T. J. Synth. Commun. 1989, 19, 529. (13) (a) Kotha, S.; Ganesh, T.; Ghosh, A. Bioorg. Med. Chem. Lett. 2000, 10, 1755. (b) Kotha, S.; Ghosh, A. K. Tetrahedron Lett. 2004, 45, 2931. (c) Kotha, S.; Sreenivasachary, N. Eur. J. Org. Chem. 2001, 3375. (d) Kotha, S.; Dhurke, K.; Khedkar, P. Synthesis 2007, 3357. (e) Kotha, S.; Khedkar, P.; Ghosh, A. K. Eur. J. Org. Chem. 2005, 3581. (f) Kotha, S.; Banerjee, S. Synthesis 2007, 1015. (g) Kotha, S.; Misra, S.; Krishna, N. G.; Devunuri, N.; Hopf, H.; Keecherikunne, A. Heterocycles 2010, 80, 847.

Benzosultine-sulfone 5 has been prepared as a o-xylylene or o-quinodimethane precursor by utilization of rongalite. Thermal activation of this hybrid molecule 5 has resulted a new sulfone-based building block 6. Building block 5 is a suitable precursor for the synthesis of unsymmetrically functionalized polycyclics through Diels-Alder (DA) chemistry. The dibromosulfone 24 and benzosultine-sulfone 5 has also been used for the synthesis of various sulfone based unnatural R-amino acid (AAA) derivatives.

DOI: 10.1021/jo100655c r 2010 American Chemical Society

Published on Web 05/24/2010

J. Org. Chem. 2010, 75, 4319–4322

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JOC Note

Kotha and Chavan

SCHEME 1.

Strategies for New o-Xylylene Precursors

SCHEME 2.

Symmetrical Bis(o-xylylene) Precursors

envisioned a hybrid molecule such as benzosultine-sulfone 5 as a useful building block for the synthesis of densely functionalized unsymmetrical polycycles. For example, by opening the sultine and sulfone portion of this hybrid molecule 5 in a stepwise manner at different temperatures and trapping the resulting o-xylylene intermediate with appropriate dienophiles, one can generate unsymmetrical polycyclics. It is worth mentioning that here the temperature of the reaction is used as regiocontrol element. In view of these interesting possibilities, o-xylylene derivatives 6 and 8 are worthwhile targets. Moreover, these building blocks are also useful to generate a library of sulfone and BCB derivatives respectively. In this regard, recently we have demonstrated that the transient intermediate 8 can be generated either from 9 or from 10.4 Herein, we report the synthesis of 5, a potential precursor for sulfone containing o-xylylene moiety 6 (Scheme 1). It is interesting to note that various sulfone derivatives can be alkylated by carbanion chemistry, and then the resulting alkylated sulfones can undergo DA chemistry with appropriate dienophiles to generate complex polycyclics. Chung and co-workers had reported the synthesis of benzodisultine 12 from the R,R0 ,R00 ,R000 -tetrabromo durene 11 via rongalite and explored its DA chemistry with various dienophiles.14 Cava and co-workers had reported the synthesis of benzodisulfone 13 by the oxidation of corresponding disulfide by cold peracetic acid.10 The benzodisulfone 13 on thermal extrusion of two molecules of sulfur dioxide gives the benzodicyclobutene 1411 (Scheme 2). Generally, thermal activation of the sultine 3 generates the o-QDM 1 at around 100 °C and sulfone 2 or cyclobutene 4 derivatives open up at higher temperature (180-200 °C). Subsequently, we realized that the o-xylylene intermediate generated from the sultine 3 can be trapped with dienophile containing an AAA moiety (e.g., methyl 2-acetamidoacrylate). Toward the synthesis of intricate polycycles and unusual AAA derivatives, dibromo derivative 18 was identified as a key intermediate (Scheme 3) that can be assembled by the DA reaction of dimethyl acetylenedicarboxylate (DMAD) and 2,3-dimethylenebutane-1,4-ditosylate 16a. The required diene 16a was prepared by cross-enyne metathesis of but-2-yne-1,4-ditosylate15 15a with Grubbs second generation catalyst in 80% yield. Unfortunately, the diene 16a did not undergo DA reaction with DMAD under a (14) Wu, An.-T.; Liu, W.-D.; Chung, W.-S. J. Chin. Chem. Soc. 2002, 49, 77 (Only one regioisomer (i.e. 12) is shown here. However, two isomers are reported). (15) Eglinton, G.; Whiting, M. C. J. Chem. Soc. 1950, 3650.

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SCHEME 3. Preparation of Dimethyl 4,5-Bis(bromomethyl)phthalate 18a

a Reagents and conditions: (a) Grubbs catalyst (5 mol %), ethylene, DCM, rt, 48 h; (b) DMAD, toluene, reflux, 24 h; (c) DDQ, benzene, reflux, 30 h or MnO2, dioxane, reflux, 72 h, 90%; (d) 10 equiv 33% HBr in acetic acid, DCM, rt, 36 h, 46%; (e) DMAD, benzene, reflux, 24 h; (f) DDQ, benzene, reflux, 30 h or MnO2, dioxane, reflux, 60 h, 75%; (g) NBS, benzoyl peroxide, CCl4, reflux, 7 h, 25%; (h) NBS, benzoyl peroxide, DCE or R,R,Rtrifluorotoluene (0.1 M), 12 h, 73%.

variety of reaction conditions (e.g., toluene, reflux; toluene, BF3etherate, 0 °C; toluene, hydroquinone, reflux; microwave irradiation). Then, we tried the DA reaction of the diene 16a with various other dienophiles under different conditions, but none of the dienophiles gave the required DA adduct. Then, we speculated that the bulky tosylate group present in the diene 16a may be responsible for the failure of the DA reaction. To address this issue, the hydroxyl groups present in but-2-yne-1,4-diol were protected as acetyl groups, and the cross-enyne metathesis of the resulting but-2-yne 1,4-diacetate 15b by Grubbs first generation catalyst in DCM at rt gave the 2,3-dimethylene butane-1,4diacetate 16b in good yield.16 Later, the DA reaction of 16b with DMAD in toluene followed by aromatization with MnO2 in dry dioxane gave the dimethyl 4,5-bis(acetoxymethyl) phthalate 17. Next, the diacetate 17 was converted to dimethyl 4,5-bis(bromomethyl)phthalate 18 by treating it with 33% HBr in acetic acid at rt in DCM using the known protocol.17 This reaction gave an acceptable yield in a small scale reaction; however, in large scale, poor yield of the desired product along with 4,5-bis(bromomethyl)phthalic acid as a side product was observed. Later, when the 4,5-bis(bromomethyl)phthalic acid was subjected to acid-catalyzed esterification, dimethyl 4,5-(methoxymethyl) phthalate was obtained. Alternatively, the dibromo derivative 18 was also prepared by the DA reaction of 2,3-dimethyl butadiene 19 and DMAD in benzene followed by the aromatization of the resulting DA adduct with DDQ in benzene (or with MnO2 in dry dioxane) to give the dimethyl 4,5-(dimethyl)phthalate 20.18 Next, benzylic bromination of 20 mediated by NBS in dry CCl4 involving a radical mechanism gave the expected dimethyl 4,5-bis(bromomethyl)phthalate 18 in 25% yield.19 Later, it was found that the bromination yield can be improved by using NBS and benzoyl peroxide as a radical (16) (a) Mori, M.; Kinoshita, A.; Sakakibara, N. J. Am. Chem. Soc. 1997, 119, 12388. (b) Diver, S. T.; Smulik, J. A. Org. Lett. 2000, 2, 2271. (17) Lohier, J.-F.; Wright, K.; Peggion, C.; Formaggio, F.; Toniolo, C.; Wakselmana, M.; Mazaleyrat, J.-P. Tetrahedron 2006, 62, 6203. (18) Farooq, O. Synthesis 1994, 1035. (19) Esser, B.; Bandyopadhyay, A.; Rominger, F.; Gleiter, R. Chem.; Eur. J. 2009, 15, 3368. (b) Anthony, J. E.; Swartz, C. R.; Landis, C. A.; Parkin, S. R. Proceeding of SPIE-The international Society for Optical Engineering 2005, 5940 (Organic field-effect transistors IV), 594002/1-594002/12.

JOC Note

Kotha and Chavan SCHEME 4.

Preparation of Dibromosulfone 24a

a Reagents and conditions: (a) rongalite, TBAB, DMF, 0 °C to rt, 7 h, 65%; (b) toluene, 100 °C, 7 h, 75%; (c) LiCl, KBH4, THF, reflux, 24 h, 77%; (d) PBr3, benzene, 0 °C to rt, 12 h, 73%.

SCHEME 5. Preparation of Benezosultine-sulfone and Its Regioselective DA Reaction at the Sultine Terminusa

a Reagents and conditions: (a) rongalite, TBAB, DMF, 0 °C to rt, 7 h, 55%; (b) DMAD, toluene, reflux, 24 h; (c) MnO2, dioxane, reflux, 72 h, 90%; (d) methyl 2-acetamidoacrylate, toluene, reflux, 24 h.

initiator in 1,2-dichloroethane (DCE) or R,R,R-trifluorotoluene (0.1 M solution) (Scheme 3). When the compound 18 was treated with rongalite in the presence of PTC such as tetrabutylammonium bromide (TBAB) in DMF at 0 °C, the sultine derivative 21 was obtained in good yield. Later the compound 21 was converted to the sulfone derivative 22 by heating in toluene at 100 °C for 7 h. Based on Anderson’s observation,20 the reduction of diester containing sulfone 22 was achieved by using KBH4, LiCl in refluxing THF to generate the corresponding diol 23 in good yield. The dihydroxysulfone 23 was then treated with phosphorus tribromide in benzene at 0 °C to deliver the dibromosulfone 24 in 73% yield (Scheme 4). Next, the dibromide 24 was converted to the desired benzosultine-sulfone 5 by treatment with rongalite in presence of TBAB in DMF at 0 °C. Having prepared the key building block 5 in 55% yields, next we explored its utility by selective opening of sultine portion and reacting the resulting o-xylylene intermediate with DMAD and methyl 2-acetamidoacrylate to generate the corresponding sulfone-based building blocks. When the benzosultine-sulfone 5 was reacted with DMAD in refluxing toluene, the desired DA adduct was obtained in good yield, which was further aromatized with freshly activated MnO2 in dry dioxane to obtain the sulfone-based diester 25 in 90% yield. Similarly, when the benzosultine-sulfone 5 was reacted with methyl 2-acetamidoacrylate in refluxing toluene, the desired tetraline-based AAA derivative 26 was obtained in a moderate yield (57%) along with rearranged benzodisulfone 13 (40%) as a side product. These sulfone derivatives 25 and 26 can be further utilized to design various polycyclics and unusual AAA derivatives (Scheme 5). Our initial attempts to open up the (20) Anderson, W. K.; Mach, R. H. Synth. Commun. 1986, 16, 911.

SCHEME 6. rivativesa

Preparation of Sulfone-Based Unusual AAA De-

a Reagents and conditions: (a) diethyl acetamidomalonate, K2CO3, MeCN, 12 h, reflux, 62%; (b) (i) ethyl isocyanoacetate, K2CO3, TBAHS, MeCN, 20 h, reflux; (ii) 4-5 drops of conc HCl, EtOH, rt, 9 h; (iii) DMAP, acetic anhydride, DCM, rt, 24 h, 52% (overall yield).

sulfone side were not successful. We are exploring alternate conditions in this direction. Alternatively, the dibromosulfone 24 has also been used for the synthesis of sulfone-based AAA derivatives 27 and 28.3 When the dibromosulfone 24 was treated with diethyl acetamidomalonate13g in dry acetonitrile in presence of K2CO3 as a base, the sulfone based 1, 2, 3, 4-tetrahydroisoquinoline-3-carboxylic acid (Tic) derivative 27 was obtained in good yield. Similarly, treating the dibromosulfone 24 with ethyl isocyanoacetate21 in dry acetonitrile in the the presence of base such as K2CO3, gave the coupling product, which on hydrolysis and protection using acetic anhydride in presence of DMAP gave the indane based AAA derivative 28. Because some of the isocyanonitrile derivatives are unstable, its isolation and characterization was not attempted. The corresponding AAA derivative 28 was prepared. These sulfone derivatives 27 and 28 serve as advanced building blocks for further synthetic manipulation to design various unusual AAA derivatives (Scheme 6). A new methodology has been devised for the synthesis of benzosultine-sulfone 5, as a useful building block suitable for DA strategy. This hybrid molecule 5 contains two latent o-QDM intermediates of different reactivity. The selective DA reaction at sultine terminus has delivered the sulfonebased precursors, which may be suitable for the synthesis of various polycyclics and unusual AAA derivatives. Experimental Section Prepareation of Benzosultine-sulfone 5. To a suspension of rongalite (2.39 g, 15.5 mmol) in DMF (15 mL) were added TBAB (501 mg, 1.55 mmol) and 4,5-bis(bromomethyl)benzosulfone 24 (550 mg, 1.55 mmol) at 0 °C, and the stirring was continued for 4 h at 0 °C. Then, the reaction mixture was brought to rt, and the stirring was continued for an additional 4 h. After completion of the reaction (TLC monitoring), the reaction mixture was diluted with ethyl acetate and washed with water (3-4 times). The aqueous layer was again extracted with ethyl acetate and the combined organic layer was washed with brine, dried over Na2SO4, and concentrated under reduced pressure, and the product was purified by silica gel column chromatography. Elution of the column with 60% ethyl acetate-petroleum ether gave 5 as a white solid (203 mg, 51% yield). Rf = 0.26 (silica gel, 60% EtOAcpetroleum ether). Mp dec at 185-190 °C. 1H NMR (300 MHz, CDCl3): δ 7.24 (s, 1H), 7.22 (s, 1H), 5.30 (1/2 ABq, J = 14.0 Hz, 1H), 4.97 (1/2 ABq, J = 14.0 Hz, 1H), 4.38 (s, 4H), 4.35 (d, J = 15.6 Hz, 1H), 3.61 (d, J = 15.6 Hz, 1H). 13C NMR (100 MHz, CDCl3): δ 134.5, 132.0, 131.4, 127.8, 127.3, 123.6, 62.7, 56.73, 56.71, 56.4. IR (KBr, cm-1): 2924, 2857, 1602, 1314, 1226, 1112, 726. HRMS (Q-Tof) m/z: [M þ Na]þ calcd for C10H10S2O4Na 280.9918, found 280.9908 (21) Kotha, S.; Halder, S. Synlett 2010, 337.

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JOC Note Preparation of 6,7-Bis(carbomethoxy)-2,3-naphthalene-sulfone 25. To a solution of benezosultine-sulfone 5 (42 mg, 0.581 mmol) in toluene (15 mL), DMAD (124 mg, 0.827 mmol) was added under N2 atmosphere, and the reaction mixture was refluxed for 36 h. After completion of the reaction (TLC monitoring), the reaction mixture was cooled, and the solvent was evaporated under reduced pressure. The crude DA adduct was directly aromatized without any further purification. This crude DA-adduct was dissolved in dry dioxane (25 mL) and treated with 70 equiv of MnO2 (970 mg). Then the reaction mixture was refluxed for 72 h, and the reaction mixture was filtered through Buchner funnel and washed (2-3 times) with ethyl acetate. The combined organic layer was concentrated under reduced pressure, and the product was purified by silica gel column chromatography. Elution of the column with 30% ethyl acetate-petroleum ether gave 25 (40 mg, 90% overall yield). Rf = 0.42 (silica gel, 60% EtOAc-petroleum ether). Mp 226-228 °C. 1H NMR (400 MHz, CDCl3): δ 8.22 (s, 2H), 7.88 (s, 2H), 4.55 (s, 4H), 3.97 (s, 6H). 13C NMR (100 MHz, CDCl3): δ 167.8, 133.1, 132.2, 129.9, 129.7, 126.3, 56.5, 53.1. IR (KBr, cm-1): 2956, 1720, 1458, 1317, 1290, 1126. HRMS (Q-Tof) m/z: [M þ Na]þ calcd for C16H14SO6Na 357.0408, found 357.0424 Preparation of Sulfone-Based Tetraline AAA Derivative 26. A solution of benzosultine-sulfone 5 (40 mg, 0.155 mmol) and methyl 2-acetamidoacrylate (33 mg, 0.233 mmol) in toluene (10 mL) was refluxed for 24 h. After completion of the reaction (TLC monitoring), the reaction mixture was brought to rt, and

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Kotha and Chavan the solvent was removed under reduced pressure. The insoluble material was washed (2-3 times) with DCM. The DCM fraction was concentrated and charged on silica gel column chromatography. Elution of the column with 70% ethyl acetatepetroleum ether gave 26 as a white crystalline product (30 mg, 57% yield). Rf = 0.19 (silica gel, 70% EtOAc-petroleum ether). Mp 238-240 °C. The insoluble material was again washed with ethyl acetate to obtain the pure benzodisulfone 13 (16 mg, 40%). 1 H NMR (400 MHz, CDCl3): δ 7.08 (s, 1H), 7.03 (s, 1H), 5.66 (s, 1H, NH), 4.33 and 4.29 (ABq, J = 16.0 Hz, 4H), 3.76 (s, 3H), 3.35 (1/2 ABq, J = 17.2 Hz, 1H), 3.03 (1/2 ABq, J = 17.2 Hz, 1H), 2.90-2.80 (m, 2H), 2.52-2.48 (m, 1H), 2.18-2.11 (m, 1H), 1.96 (s, 3H). 13C NMR (100 MHz, CDCl3): δ 173.7, 170.4, 136.0, 133.8, 129.6, 129.3, 127.0, 126.5, 57.8, 56.8, 52.9, 37.7, 28.5, 25.4, 23.3. IR (KBr, cm-1): 3297, 2925, 1737, 1651, 1542, 1315, 1238, 1127. HRMS (Q-Tof) m/z: [M þ Na]þ calcd for C16H19NSO5Na 360.0881, found 360.0890.

Acknowledgment. We thank CSIR and DST, New Delhi for financial support and SAIF, Mumbai for recording the spectral data. A.C. thanks CSIR, New Delhi for award of the research fellowship. Supporting Information Available: Detailed experimental procedures and characterization data with copies of 1H and 13C NMR spectra for all new compounds. This material is available free of charge via the Internet at http://pubs.acs.org.